CN110676331A - Preparation method of antimony sulfide thin film based on alcohol solvent and application of antimony sulfide thin film in solar cell - Google Patents
Preparation method of antimony sulfide thin film based on alcohol solvent and application of antimony sulfide thin film in solar cell Download PDFInfo
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- CN110676331A CN110676331A CN201910816652.5A CN201910816652A CN110676331A CN 110676331 A CN110676331 A CN 110676331A CN 201910816652 A CN201910816652 A CN 201910816652A CN 110676331 A CN110676331 A CN 110676331A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002904 solvent Substances 0.000 title claims abstract description 24
- 239000010409 thin film Substances 0.000 title claims description 19
- 239000000243 solution Substances 0.000 claims abstract description 108
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 93
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 54
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000004528 spin coating Methods 0.000 claims abstract description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 229910052959 stibnite Inorganic materials 0.000 claims abstract description 21
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 15
- 125000004429 atom Chemical group 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 230000005540 biological transmission Effects 0.000 claims abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 95
- 239000011521 glass Substances 0.000 claims description 81
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 19
- 239000010408 film Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 35
- 239000002002 slurry Substances 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 238000004506 ultrasonic cleaning Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 17
- 238000000861 blow drying Methods 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000009832 plasma treatment Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000010355 oscillation Effects 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000007790 scraping Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000013082 photovoltaic technology Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 231100000404 nontoxic agent Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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Abstract
The invention discloses a preparation method of an antimony sulfide film based on an alcohol solvent and application of the antimony sulfide film in a solar cell. By reacting SbCl3And thiourea according to Sb: dissolving S atom ratio of 1:1.6 in mixed solution of ethylene glycol and isopropanol or mixed solvent of ethylene glycol and ethanol or ethylene glycol solvent to prepare Sb with Sb atom concentration of 1.0-1.5M2S3Clarifying the stable solution; then prepared Sb2S3Dropping the solution on the substrate or the electron transmission layer, and spin-coating to form a uniform liquid film; and finally, carrying out preheating treatment on the rotated sample to volatilize the solvent, and carrying out high-temperature crystallization reaction to obtain the antimony sulfide film. The invention is based onSb obtained by the kind of the solvent, the kind of the solute and the proportion2S3A clear and stable solution is not only environment-friendly, but also the obtained Sb is utilized2S3The effective Sb is successfully prepared from the clear and stable solution2S3The solar cell device has great reference significance for realizing the commercialization of the photovoltaic industry by using a nontoxic reagent to replace a toxic reagent.
Description
Technical Field
The invention relates to the technical field of photoelectric material and thin film solar cell preparation, in particular to a preparation method of an antimony sulfide thin film based on an alcohol solvent and application of the antimony sulfide thin film in a solar cell.
Background
The problems of energy shortage and environmental pollution in the world are increasingly prominent nowadays, and the search of novel clean, environment-friendly and sustainable energy becomes important work in the scientific research community. Solar energy has become an important part of energy used by human beings as a basic source of earth energy with the gradual decrease of fossil fuels, and is continuously developed. The solar energy is utilized in a photo-thermal conversion mode and a photoelectric conversion mode, and solar power generation is a new renewable energy source. The photovoltaic technology is a technology capable of directly converting solar light energy into electric energy, and a photovoltaic cell manufactured by the technology is convenient to use. The photovoltaic technology-based solar cell technology cannot cause environmental pollution in the conversion process, can provide clean and environment-friendly electric energy, and is a clean and efficient power generation mode. At present, the solar cell market is mainly occupied by silicon-based solar cells due to high photoelectric conversion efficiency and mature industrial processes. However, the silicon-based solar cell has a limitation in its long-term use due to its large energy consumption, low raw material utilization rate and inability to achieve flexibility in the production process.
Antimony sulfide (Sb)2S3) The material is a novel photovoltaic material, has a high light absorption coefficient (alpha ≈ 10^5cm ^ -1), has a proper band gap width, is easy to regulate and control (1.5-2.2eV), has a light absorption range covering most visible light regions, and is considered to be one of the most promising solar cell materials.
At present, Sb is prepared by a solution spin coating method2S3The solar cell technology is mature, common solvents include DMF (dimethyl formamide), DMSO (dimethyl sulfoxide) and the like, and the common solvents have high solubility through solvent recombination, so that the photoelectric conversion efficiency of the prepared solar cell is higher, but the solvents have certain toxicity, have obvious negative effects on human bodies and the environment, and are spin-coated. Thus, novel non-toxic or low-toxic tests are usedThe preparation of the antimony sulfide thin-film solar cell by using the agent as a solution spin-coating method becomes the key point in the research work of the antimony sulfide solar cell, but how to use a non-toxic agent to replace a toxic agent and ensure that Sb is2S3The effectiveness of solar cell devices is a key problem which needs to be solved at present.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of an antimony sulfide thin film based on an alcohol solvent.
The invention also aims to provide application of the preparation method in preparation of solar cells.
The above object of the present invention is achieved by the following technical solutions:
based on the aim of searching a more environment-friendly solvent for preparing the antimony sulfide solar cell, the invention provides a novel antimony sulfide solution formula, and explores a preparation process for preparing an antimony sulfide film based on the novel solution, so that a complete and effective solar cell device can be prepared.
The solution formula takes antimony chloride and thiourea as solutes, a mixed solution of ethylene glycol and isopropanol or a mixed solution of ethylene glycol and ethanol or ethylene glycol as solvents, and SbCl3And thiourea according to Sb: dissolving S atom ratio of 1:1.6 in the alcohol solvent to obtain Sb with Sb atom concentration of 1.0-1.5M2S3The solution was clear and stable. And the Sb prepared by the novel green solvent of the formula2S3A solar cell active device.
Based on the novel solution formula, the invention provides a preparation method of an antimony sulfide film based on an alcohol solvent, which comprises the following steps:
s1, mixing SbCl3And thiourea according to Sb: dissolving S atom ratio of 1:1.6 in mixed solution of ethylene glycol and isopropanol or mixed solvent of ethylene glycol and ethanol or ethylene glycol to prepare Sb with Sb atom concentration of 1.0-1.5M2S3Clarifying the stable solution;
s2, Sb prepared in the step S12S3The solution is dropped inSpin-coating the substrate or the electron transport layer to form a uniform liquid film;
s3, preheating the sample spun in the step S2 to volatilize the solvent, and then carrying out high-temperature crystallization reaction to obtain the antimony sulfide film.
Preferably, the volume ratio of the ethylene glycol to the isopropanol or the ethylene glycol in the mixed solution of the ethylene glycol and the isopropanol and the mixed solution of the ethylene glycol and the ethanol is 3-4: 5-6.
Preferably, the electron transport layer in step S2 is TiO2And (3) a layer.
Preferably, in the step S2, 120 μ L Sb is adopted as the spin coating process2S3The solution was held at 2500rpm for 30s and at 5000rpm for 60 s.
Preferably, the preheating in step S3 is performed at 90-100 deg.C (preferably 95 deg.C) for 10-15 min (preferably 15min), and then at 180-220 deg.C (preferably 200 deg.C) for 2-4 min (preferably 2 min).
Preferably, the high-temperature crystallization reaction in step S3 is 280-320 ℃ (preferably 300 ℃) for 8-12 min (preferably 10 min).
The invention also claims the antimony sulfide film prepared by any one of the preparation methods.
The invention protects the application of the antimony sulfide film or the preparation method of the antimony sulfide film in the preparation of solar cells.
The invention also provides an antimony sulfide thin film solar cell, which contains any antimony sulfide thin film.
Preferably, the conductive substrate is FTO transparent conductive glass or ITO transparent conductive glass.
Preferably, the solar cell has a structure of glass/FTO/TiO2/Sb2S3/C or glass/FTO/TiO2/Sb2S3HTM/Ag or glass/FTO/TiO2/Sb2S3/HTM/C。
The invention also provides the glass/FTO/TiO2/Sb2S3The preparation method of the/C solar cell comprises the following steps:
s1, carrying out conventional pretreatment on FTO glass;
s2, adopting TiO2As an electron transport material, a layer of compact TiO is prepared on FTO glass in sequence2A layer and a layer of porous TiO2Layer to obtain glass/FTO/TiO2；
S3, preparing the glass/FTO/TiO by using any one of the preparation methods2Preparing a layer of Sb by spin-coating2S3Film to obtain glass/FTO/TiO2/Sb2S3。
S4, in glass/FTO/TiO2/Sb2S3Preparing carbon electrode to obtain glass/FTO/TiO2/Sb2S3A/C solar cell.
The glass/FTO/TiO2/Sb2S3the/C solar cell has no hole transport layer, short manufacturing period, rapidness and convenience.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel antimony sulfide solution formula, which is a clear and stable solution obtained based on specific solvent types, solute types and proportions, wherein the adopted solvents are mixed solution of ethylene glycol and isopropanol, mixed solution of ethylene glycol and ethanol or alcohol reagents with low toxicity or slight toxicity, the antimony sulfide solution formula is environment-friendly, the antimony sulfide solution formula has slight harm to human bodies, and the solvents and the solutes are common and cheap chemical reagents; obtained Sb2S3The clear stable solution can successfully prepare effective Sb2S3A solar cell device; simultaneously provided glass/FTO/TiO 2/Sb2S3the/C solar cell device has no hole transport layer, short manufacturing period, rapidness and convenience, and can save the cost of an expensive organic hole transport layer, so that the manufacturing cost of the whole device is lower; the invention finally obtains an effective device with the highest photoelectric conversion efficiency of 0.8 percent. The invention has great reference significance for realizing the commercialization of the photovoltaic industry by using a nontoxic reagent to replace a toxic reagent.
Drawings
FIG. 1 shows the glass/FTO/TiO 2/Sb of the antimony sulfide solar cell device2S3Structure of the/C diagram.
FIG. 2 is a J-V diagram of the device made in example 1.
FIG. 3 is a J-V diagram of the device made in example 2.
FIG. 4 is a J-V diagram of a device made in example 3.
FIG. 5 is a J-V diagram of a device made in example 4.
Fig. 6 is a J-V diagram of a device made in comparative example 3, with the inset being the first quadrant portion.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
Secondly, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare the compact TiO2The solution of (1). 100 μ L of the solution was spin-coated on the treated FTO transparent conductive glass at 7000rpm for 60s, and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, the mass ratio is TiO2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2The solution (2) is subjected to ultrasonic oscillation for 30 min. Taking 80 μ L of the solution to glass/FTO/bl-TiO2The substrate was spin-coated at 2000rpm for 30s and then placed on a heated platen at 550 ℃ for 30 min.
Fourthly, the treated glass/FTO/bl-TiO is treated2/mp-TiO2The mixture was placed in a 40ml +0.3035ml TiCl solution4The mixed solution of (3) was left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and then rinsingThe mixture was placed on a heating stage at 450 ℃ and reacted for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 in mixed solvent of ethylene glycol and isopropanol with volume ratio of 4:5 to prepare solution with Sb atom concentration of 1.5M, stirring, shaking and filtering until the solution is clear. Dropping 120 μ L of the solution on the glass/FTO/bl-TiO treated in the fourth step2/mp-TiO2The liquid was spin coated using a spin coating process of 2500rpm 30s, 5000rpm 60 s. The sample after spin coating is placed on a hot bench and is respectively heated at 95 ℃ for 15min, 200 ℃ for 2min and 300 ℃ for 10 min.
And sixthly, covering the prepared sample by using a pre-prepared mask plate, coating carbon electrodes on the surface of the sample and the surface of the FTO by using carbon slurry in a scraping way, and then placing the sample and the FTO on a heating table at 100 ℃ for 30-60min to dry the carbon slurry to form the solid carbon electrode. The glass/FTO/TiO obtained2/Sb2S3The structure of the/C solar cell is shown in figure 1. The photoelectric conversion efficiency of the cell is shown in fig. 2, resulting in an effective device with a photoelectric conversion efficiency of 0.82%.
Example 2
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
Secondly, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare the compact TiO2The solution of (1). 100 μ L of the solution was spin-coated on the treated FTO transparent conductive glass at 7000rpm for 60s, and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, mixing TiO with the mixture according to the weight ratio2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2The solution (2) is subjected to ultrasonic oscillation for 30 min. Taking 80 μ L of the solution to glass/FTO/bl-TiO2The substrate was spin-coated at 2000rpm for 30s and then placed on a heated platen at 550 ℃ for 30 min.
Fourthly, the treated glass/FTO/bl-TiO is treated2/mp-TiO2Is arranged at 40ml+0.3035ml TiCl4The mixed solution of (3) was left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and placing on a heating table at 450 ℃ for reaction for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 in mixed solvent of ethylene glycol and isopropanol with volume ratio of 4:5 to prepare solution with Sb atom concentration of 1.5M, stirring, shaking and filtering until the solution is clear. Dropping 120 μ L of the solution on the glass/FTO/bl-TiO treated in the fourth step2/mp-TiO2The liquid was spin coated using a spin coating process of 2500rpm 30s, 5000rpm 60 s. Placing in a vacuum chamber for 5min, placing the sample on a hot stage, and heating at 95 deg.C for 15min, 200 deg.C for 2min, and 300 deg.C for 10 min.
And sixthly, covering the prepared sample by using a pre-prepared mask plate, coating carbon electrodes on the surface of the sample and the surface of the FTO by using carbon slurry in a scraping way, and then placing the sample and the FTO on a heating table at 100 ℃ for 30-60min to dry the carbon slurry to form the solid carbon electrode. As shown in fig. 3, an effective device having a photoelectric conversion efficiency of 0.27% was obtained.
Example 3
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
Secondly, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare the compact TiO2The solution of (1). 100 μ L of the solution was spin-coated on the treated FTO transparent conductive glass at 7000rpm for 60s, and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, mixing TiO with the mixture according to the weight ratio2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2The solution (2) is subjected to ultrasonic oscillation for 30 min. Taking 80 μ L of the solution to glass/FTO/bl-TiO2The substrate was spin-coated at 2000rpm for 30s and then placed on a heated platen at 550 ℃ for 30 min.
Fourthly, the treated glass/FTO/bl-TiO is treated2/mp-TiO2The mixture was placed in a 40ml +0.3035ml TiCl solution4The mixed solution of (3) was left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and placing on a heating table at 450 ℃ for reaction for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 in mixed solvent of ethylene glycol and isopropanol with volume ratio of 4:5 to prepare solution with Sb atom concentration of 1.5M, stirring, shaking and filtering until the solution is clear. Dropping 120 μ L of the solution on the glass/FTO/bl-TiO treated in the fourth step2/mp-TiO2The liquid was spin coated using a spin coating process of 2500rpm 30s, 5000rpm 60 s. The sample after spin coating is placed on a hot bench and is respectively heated at 95 ℃ for 15min, 200 ℃ for 2min and 400 ℃ for 10 min.
And sixthly, covering the prepared sample by using a pre-prepared mask plate, coating carbon electrodes on the surface of the sample and the surface of the FTO by using carbon slurry in a scraping way, and then placing the sample and the FTO on a heating table at 100 ℃ for 30-60min to dry the carbon slurry to form the solid carbon electrode. As shown in fig. 4, an effective device having a photoelectric conversion efficiency of 0.53% was obtained.
Example 4
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
Secondly, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare the compact TiO2The solution of (1). 100 μ L of the solution was spin-coated on the treated FTO transparent conductive glass at 7000rpm for 60s, and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, mixing TiO with the mixture according to the weight ratio2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2The solution (2) is subjected to ultrasonic oscillation for 30 min. Taking 80 μ L of the solution to glass/FTO/bl-TiO2The substrate was spin-coated at 2000rpm for 30s and then placed on a heated platen at 550 ℃ for 30 min.
Fourthly, the treated glass/FTO/bl-TiO is treated2/mp-TiO2The mixture was placed in a 40ml +0.3035ml TiCl solution4The mixed solution of (3) was left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and placing on a heating table at 450 ℃ for reaction for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 in mixed solvent of ethylene glycol and isopropanol with volume ratio of 4:5 to prepare solution with Sb atom concentration of 1.5M, stirring, shaking and filtering until the solution is clear. Dropping 120 μ L of the solution on the glass/FTO/bl-TiO treated in the fourth step2/mp-TiO2The liquid was spin coated using a spin coating process of 2500rpm 30s, 5000rpm 60 s. The sample after spin coating is placed on a hot bench and is respectively heated at 95 ℃ for 15min, 200 ℃ for 2min and 300 ℃ for 10 min.
In the sixth step, 36.6mg of Spiro-OMeTAD powder, 14. mu.L of tBP, 9.5. mu.L of 520mg/ml Li-TFSI/acetonitrile solution and 1ml of chlorobenzene were mixed and stirred to prepare a mixed solution of the hole transport layer HTM. 100 mul of the solution was dropped on the surface of the sample which had been heat treated before, spin-coated at 3000rpm for 30s, and then placed on a 100 ℃ hot stage for 10min to obtain a hole transport layer.
And step seven, covering the prepared sample by using a prepared mask plate, scraping and coating carbon electrodes on the surface of the sample and the surface of the FTO by using carbon paste, and then placing the sample and the FTO on a heating table at 100 ℃ for 30-60min to dry the carbon paste to form the solid carbon electrode. As shown in fig. 5, an effective device having a photoelectric conversion efficiency of 0.26% was obtained.
Example 5
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
Secondly, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare the compact TiO2The solution of (1). 100 μ L of the solution was spin-coated on the treated FTO transparent conductive glass at 7000rpm for 60s, and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, mixing TiO with the mixture according to the weight ratio2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2The solution (2) is subjected to ultrasonic oscillation for 30 min. Taking 80 μ L of the solution to glass/FTO/bl-TiO2The substrate was spin-coated at 2000rpm for 30s and then placed on a heated platen at 550 ℃ for 30 min.
Fourthly, the treated glass/FTO/bl-TiO is treated2/mp-TiO2The mixture was placed in a 40ml +0.3035ml TiCl solution4The mixed solution of (3) was left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and placing on a heating table at 450 ℃ for reaction for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 in mixed solvent of ethylene glycol and isopropanol with volume ratio of 3:6 to prepare solution with Sb atom concentration of 1.5M, stirring, shaking and filtering until the solution is clear. Dropping 120 μ L of the solution on the glass/FTO/bl-TiO treated in the fourth step2/mp-TiO2The liquid was spin coated using a spin coating process of 2500rpm 30s, 5000rpm 60 s. The sample after spin coating is placed on a hot bench and is respectively heated at 95 ℃ for 15min, 200 ℃ for 2min and 300 ℃ for 10 min.
And sixthly, covering the prepared sample by using a pre-prepared mask plate, coating carbon electrodes on the surface of the sample and the surface of the FTO by using carbon slurry in a scraping way, and then placing the sample and the FTO on a heating table at 100 ℃ for 30-60min to dry the carbon slurry to form the solid carbon electrode.
Example 6
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
In the second step, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare a solution for preparing dense TiO 2. 100 μ L of the solution was spin-coated on the treated FTO transparent conductive glass at 7000rpm for 60s, and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, mixing TiO with the mixture according to the weight ratio2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2Solution of (2)And ultrasonically oscillating for 30 min. Taking 80 μ L of the solution to glass/FTO/bl-TiO2The substrate was spin-coated at 2000rpm for 30s and then placed on a heated platen at 550 ℃ for 30 min.
Fourthly, the treated glass/FTO/bl-TiO is treated2/mp-TiO2The mixture was placed in a 40ml +0.3035ml TiCl solution4The mixed solution of (3) was left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and placing on a heating table at 450 ℃ for reaction for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 in ethylene glycol to obtain a solution with Sb atom concentration of 1.5M, stirring, shaking, and filtering to obtain clear solution. Dropping 120 μ L of the solution on the glass/FTO/bl-TiO treated in the fourth step2/mp-TiO2The liquid was spin coated using a spin coating process of 2500rpm 30s, 5000rpm 60 s. The sample after spin coating is placed on a hot bench and is respectively heated at 95 ℃ for 15min, 200 ℃ for 2min and 300 ℃ for 10 min.
And sixthly, covering the prepared sample by using a pre-prepared mask plate, coating carbon electrodes on the surface of the sample and the surface of the FTO by using carbon slurry in a scraping way, and then placing the sample and the FTO on a heating table at 100 ℃ for 30-60min to dry the carbon slurry to form the solid carbon electrode.
Example 7
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
Secondly, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare the compact TiO2The solution of (1). 100 μ L of the solution was spin-coated on the treated FTO transparent conductive glass at 7000rpm for 60s, and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, the mass ratio is TiO2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2The solution (2) is subjected to ultrasonic oscillation for 30 min. Taking 80 μ L of the solution to glass/FTO/bl-TiO2Spin coating the substrate at 2000rpm for 30s, howeverThen placing on a heating table at 550 ℃ for 30 min.
Fourthly, the treated glass/FTO/bl-TiO is treated2/mp-TiO2The mixture was placed in a mixed solution of 40ml +0.3035ml TiCl4 and left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and placing on a heating table at 450 ℃ for reaction for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 in mixed solvent of ethylene glycol and ethanol with volume ratio of 4:5 to prepare solution with Sb atom concentration of 1.5M, stirring, shaking and filtering until the solution is clear. Dropping 120 μ L of the solution on the glass/FTO/bl-TiO treated in the fourth step2/mp-TiO2The liquid was spin coated using a spin coating process of 2500rpm 30s, 5000rpm 60 s. The sample after spin coating is placed on a hot bench and is respectively heated at 95 ℃ for 15min, 200 ℃ for 2min and 300 ℃ for 10 min.
And sixthly, covering the prepared sample by using a pre-prepared mask plate, coating carbon electrodes on the surface of the sample and the surface of the FTO by using carbon slurry in a scraping way, and then placing the sample and the FTO on a heating table at 100 ℃ for 30-60min to dry the carbon slurry to form the solid carbon electrode.
Example 8
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
Secondly, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare the compact TiO2The solution of (1). 100 μ L of the solution was spin-coated on the treated FTO transparent conductive glass at 7000rpm for 60s, and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, mixing TiO with the mixture according to the weight ratio2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2The solution (2) is subjected to ultrasonic oscillation for 30 min. Taking 80 μ L of the solution to glass/FTO/bl-TiO2The substrate was spin-coated at 2000rpm for 30s and then placed on a heated platen at 550 ℃ for 30 min.
The fourth stepMixing the above treated glass/FTO/bl-TiO2/mp-TiO2The mixture was placed in a 40ml +0.3035ml TiCl solution4The mixed solution of (3) was left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and placing on a heating table at 450 ℃ for reaction for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 in mixed solvent of ethylene glycol and isopropanol with volume ratio of 4:5 to prepare solution with Sb atom concentration of 1M, stirring, shaking and filtering until the solution is clear. Dropping 120 μ L of the solution on the glass/FTO/bl-TiO treated in the fourth step2/mp-TiO2The liquid was spin coated using a spin coating process of 2500rpm 30s, 5000rpm 60 s. The sample after spin coating is placed on a hot bench and is respectively heated at 95 ℃ for 15min, 200 ℃ for 2min and 300 ℃ for 10 min.
And sixthly, covering the prepared sample by using a pre-prepared mask plate, coating carbon electrodes on the surface of the sample and the surface of the FTO by using carbon slurry in a scraping way, and then placing the sample and the FTO on a heating table at 100 ℃ for 30-60min to dry the carbon slurry to form the solid carbon electrode.
Comparative example 1
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
Secondly, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare the compact TiO2The solution of (1). Mu.l of the solution was spun on the treated FTO transparent conductive glass at 7000rpm for 60s and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, the mass ratio is TiO2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2The solution (2) is subjected to ultrasonic oscillation for 30 min. Taking 80 μ l of the solution to glass/FTO/bl-TiO2The substrate was spin-coated at 2000rpm for 30s and then placed on a heated platen at 550 ℃ for 30 min.
Fourthly, the treated glass/FTO/bl-TiO is treated2/mp-TiO2The mixture was placed in a 40ml +0.3035ml TiCl solution4The mixed solution of (3) was left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and placing on a heating table at 450 ℃ for reaction for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 and Sb atom concentration of 1.5M in pure isopropanol, and stirring to obtain a clear solution; the antimony sulfide thin film obtained after spin coating has small grain size and poor crystallinity, and an effective solar cell device cannot be obtained.
Comparative example 2
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
Secondly, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare the compact TiO2The solution of (1). Mu.l of the solution was spun on the treated FTO transparent conductive glass at 7000rpm for 60s and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, the mass ratio is TiO2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2The solution (2) is subjected to ultrasonic oscillation for 30 min. Taking 80 μ l of the solution to glass/FTO/bl-TiO2The substrate was spin-coated at 2000rpm for 30s and then placed on a heated platen at 550 ℃ for 30 min.
Fourthly, the treated glass/FTO/bl-TiO is treated2/mp-TiO2The mixture was placed in a 40ml +0.3035ml TiCl solution4The mixed solution of (3) was left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and placing on a heating table at 450 ℃ for reaction for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 and Sb atom concentration of 1.5M in pure ethanol, and stirring to obtain a clear solution; the antimony sulfide thin film obtained after spin coating has small grain size and poor crystallinity, and an effective solar cell device cannot be obtained.
Comparative example 3
Firstly, an ultrasonic cleaning method is adopted, FTO transparent conductive glass cut into the size of 2.5cm multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning for 15min by deionized water, ethanol and acetone respectively, blow-drying is carried out by nitrogen after cleaning is finished, and then plasma treatment is carried out for 10 min.
Secondly, 0.4263g of isopropyl titanate and 0.1577g of diethanolamine are dissolved in 3ml of ethanol and stirred for 15min to prepare the compact TiO2The solution of (1). Mu.l of the solution was spun on the treated FTO transparent conductive glass at 7000rpm for 60s and then placed on a heating stage at 500 ℃ for 2 h.
Thirdly, the mass ratio is TiO2Slurry preparation: ratio of 1:4 ethanol was configured to produce porous TiO2The solution (2) is subjected to ultrasonic oscillation for 30 min. Taking 80 μ l of the solution to glass/FTO/bl-TiO2The substrate was spin-coated at 2000rpm for 30s and then placed on a heated platen at 550 ℃ for 30 min.
Fourthly, the treated glass/FTO/bl-TiO is treated2/mp-TiO2The mixture was placed in a 40ml +0.3035ml TiCl solution4The mixed solution of (3) was left at 70 ℃ for 30 min. Then respectively rinsing with deionized water and ethanol, and placing on a heating table at 450 ℃ for reaction for 30 min.
Step five, mixing SbCl3And Thiourea (TU) as Sb: dissolving S atom ratio of 1:1.6 in mixed solvent of ethylene glycol and isopropanol with volume ratio of 4:5 to prepare solution with Sb atom concentration of 1.5M, stirring, shaking and filtering until the solution is clear. Dropping 120 μ l of the solution on the glass/FTO/bl-TiO treated in the fourth step2/mp-TiO2The liquid was spin coated using a spin coating process of 2500rpm 30s, 5000rpm 60 s. The sample after spin coating is placed on a hot bench and is respectively heated at 95 ℃ for 15min, 200 ℃ for 2min and 300 ℃ for 10 min.
Sixthly, taking the sample off the hot platform, cooling, and treating by the same spin coating and heating process as the fifth step, namely taking Sb2S3Dropping 120 μ l of the solution on the sample, spin-coating the solution at 2500rpm for 30s and 5000rpm for 60s, and heating at 95 deg.C for 15min, 200 deg.C for 2min and 300 deg.C for 10 min.
And step seven, covering the prepared sample by using a prepared mask plate, scraping and coating carbon electrodes on the surface of the sample and the surface of the FTO by using carbon paste, and then placing the sample and the FTO on a heating table at 100 ℃ for 30-60min to dry the carbon paste to form the solid carbon electrode. The above method does not result in an effective device, as shown in fig. 6, without an effective J-V curve.
Claims (10)
1. A preparation method of antimony sulfide thin film based on alcohol solvent is characterized by comprising the following steps:
s1, mixing SbCl3And thiourea according to Sb: dissolving S atom ratio of 1:1.6 in mixed solution of ethylene glycol and isopropanol or mixed solvent of ethylene glycol and ethanol or ethylene glycol solvent to prepare Sb with Sb atom concentration of 1.0-1.5M2S3Clarifying the stable solution;
s2, Sb prepared in the step S12S3Dropping the solution on the substrate or the electron transmission layer, and spin-coating to form a uniform liquid film;
s3, preheating the sample spun in the step S2 to volatilize the solvent, and then carrying out high-temperature crystallization reaction to obtain the antimony sulfide film.
2. The preparation method according to claim 1, wherein the volume ratio of the ethylene glycol to the isopropanol in the mixed solution of the ethylene glycol and the isopropanol is 3-4: 5-6, and the volume ratio of the ethylene glycol to the ethanol in the mixed solution of the ethylene glycol and the ethanol is 3-4: 5-6.
3. The method of claim 1, wherein the spin coating at step S2 is performed at 2500rpm for 30S and then 5000rpm for 60S.
4. The method according to claim 1, wherein the preheating in step S3 is performed at 90-100 ℃ for 10-15 min, and then at 180-220 ℃ for 2-4 min.
5. The method according to claim 1, wherein the high temperature crystallization reaction is carried out at 280 to 320 ℃ for 8 to 12 min.
6. An antimony sulfide thin film produced by the production method according to any one of claims 1 to 5.
7. Use of the antimony sulfide thin film according to claim 6 or the preparation method according to any one of claims 1 to 5 in the preparation of a solar cell.
8. An antimony sulfide thin film solar cell comprising the antimony sulfide thin film according to claim 5.
9. The antimony sulfide thin film solar cell of claim 8, wherein the cell structure is glass/FTO/TiO2/Sb2S3/C or glass/FTO/TiO2/Sb2S3HTM/Ag or glass/FTO/TiO2/Sb2S3/HTM/C。
10. The medium glass/FTO/TiO of claim 92/Sb2S3The preparation method of the/C solar cell is characterized by comprising the following steps:
s1, carrying out conventional pretreatment on FTO glass;
s2, adopting TiO2As an electron transport material, a layer of compact TiO is prepared on FTO glass in sequence2A layer and a layer of porous TiO2Layer to obtain glass/FTO/TiO2；
S3, preparing glass/FTO/TiO by using the preparation method of any one of claims 1 to 42Preparing a layer of Sb by spin-coating2S3Film to obtain glass/FTO/TiO2/Sb2S3。
S4, in glass/FTO/TiO2/Sb2S3Preparing carbon electrode to obtain glass/FTO/TiO2/Sb2S3A/C solar cell.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112885711A (en) * | 2021-01-18 | 2021-06-01 | 中国科学院合肥物质科学研究院 | Compact Sb2S3Preparation method of thin film and solar cell based on thin film |
| CN113097314A (en) * | 2021-03-31 | 2021-07-09 | 福州大学 | Flexible antimony sulfide thin-film solar cell and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130527A (en) * | 2013-03-25 | 2013-06-05 | 武汉工程大学 | Preparation method of super-hydrophobic antimony sulfide coating |
| JP2016025330A (en) * | 2014-07-24 | 2016-02-08 | 積水化学工業株式会社 | Thin film solar cell and manufacturing method therefor |
| CN105324863A (en) * | 2013-12-11 | 2016-02-10 | 积水化学工业株式会社 | Thin-film solar cell, and production method for thin-film solar cell |
| US20160240804A1 (en) * | 2013-11-07 | 2016-08-18 | Sekisui Chemical Co., Ltd. | Coating material for forming semiconductors, semiconductor thin film, thin film solar cell and method for manufacturing thin film solar cell |
| CN106277051A (en) * | 2016-07-21 | 2017-01-04 | 中国科学院合肥物质科学研究院 | A kind of crystallinity Sb2s3the solution preparation for processing of thin film |
| CN107302057A (en) * | 2017-07-13 | 2017-10-27 | 福州大学 | Planar structure hybrid solar cell based on antimonous sulfide dense film |
| CN107892328A (en) * | 2017-11-17 | 2018-04-10 | 广西生富锑业科技股份有限公司 | A kind of preparation method of high-purity antimony trisulfide |
| CN110137272A (en) * | 2019-05-14 | 2019-08-16 | 西北工业大学深圳研究院 | A kind of preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film |
-
2019
- 2019-08-30 CN CN201910816652.5A patent/CN110676331A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130527A (en) * | 2013-03-25 | 2013-06-05 | 武汉工程大学 | Preparation method of super-hydrophobic antimony sulfide coating |
| US20160240804A1 (en) * | 2013-11-07 | 2016-08-18 | Sekisui Chemical Co., Ltd. | Coating material for forming semiconductors, semiconductor thin film, thin film solar cell and method for manufacturing thin film solar cell |
| CN105324863A (en) * | 2013-12-11 | 2016-02-10 | 积水化学工业株式会社 | Thin-film solar cell, and production method for thin-film solar cell |
| JP2016025330A (en) * | 2014-07-24 | 2016-02-08 | 積水化学工業株式会社 | Thin film solar cell and manufacturing method therefor |
| CN106277051A (en) * | 2016-07-21 | 2017-01-04 | 中国科学院合肥物质科学研究院 | A kind of crystallinity Sb2s3the solution preparation for processing of thin film |
| CN107302057A (en) * | 2017-07-13 | 2017-10-27 | 福州大学 | Planar structure hybrid solar cell based on antimonous sulfide dense film |
| CN107892328A (en) * | 2017-11-17 | 2018-04-10 | 广西生富锑业科技股份有限公司 | A kind of preparation method of high-purity antimony trisulfide |
| CN110137272A (en) * | 2019-05-14 | 2019-08-16 | 西北工业大学深圳研究院 | A kind of preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film |
Non-Patent Citations (5)
| Title |
|---|
| ZHANG, R等: "Morphology-controlled growth of crystalline antimony sulfide via a refluxing polyol process", 《JOURNAL OF CRYSTAL GROWTH》 * |
| 化学工业部天津化工研究院 等编: "《化工产品手册 无机化工产品》", 31 October 1993, 化学工业出版社 * |
| 王心怡 等: "Sb2S3太阳能电池的研究进展", 《化工进展》 * |
| 王杰: "硫化物半导体薄膜的溶液法制备及其光电性能研究", 《中国优秀硕士学位论文全文数据库（电子期刊）基础科技辑》 * |
| 蒋岚 等: "TiO2/Sb2S3/C全无机薄膜太阳电池的构筑与性能研究", 《湖州师范学院学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112885711A (en) * | 2021-01-18 | 2021-06-01 | 中国科学院合肥物质科学研究院 | Compact Sb2S3Preparation method of thin film and solar cell based on thin film |
| CN113097314A (en) * | 2021-03-31 | 2021-07-09 | 福州大学 | Flexible antimony sulfide thin-film solar cell and preparation method thereof |
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